supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

hy2090 scheme

Acta Cryst. (2007). E63, m2908-m2909    [ doi:10.1107/S1600536807054864 ]

catena-Poly[4,4'-bipyridinium [bis([mu]3-pyrazole-3,5-dicarboxylato-[kappa]5O5,N1:N2,O3:O3)dicopper(II)]]

Q.-Q. Dou, Y.-K. He, L.-T. Zhang and Z.-B. Han

Abstract top

The title compound, {(C10H10N2)[Cu2(C5HN2O4)2]}n, has been synthesized under hydrothermal conditions. The self-assembly of the pyrazole-3,5-dicarboxylate ligands and CuII atoms results in a one-dimensional anionic chain, in which the CuII atom is five-coordinate in a square-pyramidal geometry. The doubly protonated 4,4'-bipyridine (bpy) cation lies on an inversion center. A two-dimensional supramolecular network is formed through N-H...O hydrogen bonds between the bpy cations and the uncoordinated carboxylate O atoms of the polymeric anions. The dinuclear repeat unit with two bridging pyrazole rings is centrosymmetric.

Comment top

Coordination chemistry of copper(II) complexes is a subject of continuing importance in connection with the structures and their magnetic properties (Tanase et al., 2005). Particular interest has been directed towards the investigation of the copper(II) complexes, which have been intensively studied as a result of the efforts to understand the factors that are responsible for the magnetic-exchange interactions between uncoupled metal centers (Sears & Wong, 1999; Thompson, 2002; Chaudhuri, 2003; La Monica & Ardizzoia, 1997). We report here the synthesis and structure of a coordination polymer assembled by pyrazole-3,5-dicarboxylic acid (H3pydc), 4,4'-bipyridine (bpy) and CuII ion.

The asymmetric unit of the title compound contains one CuII atom, one pydc ligand and a half protonated bpy ligand. Two centrosymmetric CuII atoms are bridged by a pair of anionic pydc ligands, forming a binuclear unit. The binuclear units are further connected by O3 atoms of adjacent units to form a one-dimensional zigzag chain (Han et al., 2007). Each CuII atom is five-coordinated by three O atoms and two N atoms from three individual pydc ligands in a square-pyramidal coordination geometry (Fig. 1; Table 1). One intriguing feature of the structure is that there exist two bimetallic rings. One is a six-membered Cu2N4 ring with a Cu···Cu separation of 3.934 (3) Å. The other is a four-membered Cu2O2 ring with a Cu···Cu separation of 3.399 (3) Å. This short Cu···Cu separation is very similar to the distance observed in a structurally related copper complex recently reported (Koomen-Van Oudenniel et al., 1989). Another interesting feature is that the zigzag chains are further extended into a three-dimensional supramolecular network (Fig. 2) though N—H···O hydrogen bonds between the carboxylate O atoms of the anionic [Cu2(pydc)2] units and the protonated bpy molecules (Table 2).

Related literature top

For related literature, see: Chaudhuri (2003); Han et al. (2007); Koomen-Van Oudenniel et al. (1989); La Monica & Ardizzoia (1997); Sears & Wong (1999); Tanase et al. (2005); Thompson (2002).

Experimental top

A mixture of Cu(NO3)2·3H2O(0.120 g, 0.5 mmol), pyrazole-3,5-dicarboxylic acid (0.087 g, 0.5 mmol), 4,4'-bipyridine (0.122 g, 0.5 mmol), NaOH (0.04 g, 1 mmol) and water (10 ml) was sealed in a 23 ml Teflon-lined reactor and heated at 473 K for 6 d. After cooled to room temperature at a rate of 5 K h−1, black crystals of the title compound were obtained (yield 52%). Analysis calculated for C20H12Cu2N6O8: C 40.60, H 2.00, N 14.25%; found: C 40.62, H 2.05, N 14.21%.

Refinement top

H atoms were positioned geometrically and refined as riding, with C—H = 0.93 Å, N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. One-dimensional chain structure in the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) −x, 2 − y, 1 − z; (ii) x, y − 1, z; (iii) −x, 1 − y, 1 − z.]
[Figure 2] Fig. 2. Three-dimensional network of the title compound, showing the hydrogen-bonding interactions (dotted lines).
catena-Poly[4,4'-bipyridinium [bis(µ3-pyrazole-3,5-dicarboxylato- κ5O5,N1:N2,O3:O3)dicopper(II)]] top
Crystal data top
(C10H10N2)[Cu2(C5HN2O4)2]F000 = 592
Mr = 591.44Dx = 2.070 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2356 reflections
a = 8.1582 (18) Åθ = 2.3–25.0º
b = 6.3620 (12) ŵ = 2.31 mm−1
c = 18.679 (3) ÅT = 293 (2) K
β = 101.862 (15)ºBlock, black
V = 948.8 (3) Å30.46 × 0.35 × 0.29 mm
Z = 2
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2187 independent reflections
Radiation source: fine-focus sealed tube2032 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
T = 293(2) Kθmax = 27.5º
φ and ω scanθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→1
Tmin = 0.416, Tmax = 0.554k = −8→1
3105 measured reflectionsl = −24→24
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025  w = 1/[σ2(Fo2) + (0.0338P)2 + 0.6043P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.071(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.38 e Å−3
2187 reflectionsΔρmin = −0.36 e Å−3
164 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0249 (13)
Secondary atom site location: difference Fourier map
Crystal data top
(C10H10N2)[Cu2(C5HN2O4)2]V = 948.8 (3) Å3
Mr = 591.44Z = 2
Monoclinic, P21/cMo Kα
a = 8.1582 (18) ŵ = 2.31 mm−1
b = 6.3620 (12) ÅT = 293 (2) K
c = 18.679 (3) Å0.46 × 0.35 × 0.29 mm
β = 101.862 (15)º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2187 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2032 reflections with I > 2σ(I)
Tmin = 0.416, Tmax = 0.554Rint = 0.018
3105 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025164 parameters
wR(F2) = 0.071H-atom parameters constrained
S = 1.05Δρmax = 0.38 e Å−3
2187 reflectionsΔρmin = −0.36 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.11209 (3)0.72576 (4)0.501800 (11)0.02128 (11)
C10.3356 (2)0.7260 (3)0.63644 (10)0.0214 (4)
C20.2373 (2)0.9262 (3)0.63423 (9)0.0197 (3)
C30.2260 (2)1.1011 (3)0.67817 (9)0.0216 (4)
H3A0.28431.12660.72560.026*
C40.1067 (2)1.2288 (3)0.63437 (10)0.0201 (3)
C50.0225 (2)1.4354 (3)0.63753 (9)0.0207 (3)
C60.3833 (3)1.7140 (3)0.85036 (11)0.0309 (4)
H6A0.40111.82920.82230.037*
C70.4729 (3)1.6925 (3)0.92106 (11)0.0267 (4)
H7A0.54941.79560.94130.032*
C80.4491 (2)1.5165 (3)0.96242 (9)0.0202 (3)
C90.3284 (2)1.3702 (3)0.93080 (10)0.0271 (4)
H9A0.30781.25250.95710.033*
C100.2399 (3)1.4006 (4)0.86062 (10)0.0303 (4)
H10A0.15841.30430.83960.036*
N10.1315 (2)0.9517 (2)0.56971 (8)0.0244 (3)
N20.0535 (2)1.1346 (2)0.56948 (8)0.0248 (3)
N30.2707 (2)1.5681 (3)0.82268 (8)0.0301 (4)
H3B0.21581.58260.77850.036*
O10.29805 (16)0.6162 (2)0.57641 (7)0.0238 (3)
O20.44127 (18)0.6763 (3)0.69028 (8)0.0318 (3)
O3−0.07916 (17)1.4892 (2)0.57719 (7)0.0255 (3)
O40.04633 (18)1.5447 (2)0.69333 (7)0.0278 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02635 (15)0.01578 (14)0.01696 (14)0.00340 (8)−0.00663 (9)−0.00196 (7)
C10.0207 (8)0.0222 (9)0.0194 (8)0.0004 (7)0.0000 (7)0.0038 (7)
C20.0210 (8)0.0208 (8)0.0147 (7)−0.0008 (7)−0.0027 (6)0.0023 (6)
C30.0230 (8)0.0251 (9)0.0144 (7)0.0003 (7)−0.0018 (6)0.0003 (7)
C40.0233 (8)0.0193 (8)0.0155 (8)−0.0017 (7)−0.0009 (7)−0.0013 (6)
C50.0225 (8)0.0202 (8)0.0179 (7)−0.0012 (7)0.0006 (6)−0.0021 (7)
C60.0363 (11)0.0330 (11)0.0225 (9)0.0010 (9)0.0040 (8)0.0058 (8)
C70.0286 (9)0.0272 (10)0.0227 (9)−0.0055 (8)0.0013 (7)0.0019 (8)
C80.0197 (8)0.0250 (9)0.0157 (8)−0.0004 (7)0.0029 (6)−0.0009 (7)
C90.0274 (9)0.0317 (10)0.0207 (8)−0.0073 (8)0.0012 (7)0.0009 (8)
C100.0287 (9)0.0371 (11)0.0225 (8)−0.0053 (8)−0.0010 (7)−0.0052 (8)
N10.0309 (8)0.0176 (7)0.0194 (7)0.0046 (6)−0.0072 (6)−0.0014 (6)
N20.0324 (8)0.0170 (7)0.0194 (7)0.0051 (6)−0.0079 (6)−0.0018 (6)
N30.0312 (8)0.0412 (10)0.0150 (7)0.0046 (8)−0.0020 (6)0.0002 (7)
O10.0253 (6)0.0223 (7)0.0205 (6)0.0054 (5)−0.0029 (5)−0.0010 (5)
O20.0312 (7)0.0358 (8)0.0227 (6)0.0097 (6)−0.0075 (6)0.0022 (6)
O30.0297 (7)0.0214 (6)0.0206 (6)0.0056 (5)−0.0062 (5)−0.0051 (5)
O40.0327 (7)0.0286 (7)0.0189 (6)0.0043 (6)−0.0020 (5)−0.0061 (5)
Geometric parameters (Å, °) top
Cu1—N11.9021 (16)C6—N31.333 (3)
Cu1—N2i1.9099 (15)C6—C71.378 (3)
Cu1—O11.9647 (13)C6—H6A0.9300
Cu1—O3i1.9889 (13)C7—C81.397 (3)
Cu1—O3ii2.7543 (15)C7—H7A0.9300
C1—O21.224 (2)C8—C91.395 (3)
C1—O11.303 (2)C8—C8iii1.492 (3)
C1—C21.501 (3)C9—C101.374 (3)
C2—N11.340 (2)C9—H9A0.9300
C2—C31.397 (3)C10—N31.332 (3)
C3—C41.396 (3)C10—H10A0.9300
C3—H3A0.9300N1—N21.326 (2)
C4—N21.342 (2)N2—Cu1i1.9099 (15)
C4—C51.490 (2)N3—H3B0.8600
C5—O41.235 (2)O3—Cu1i1.9889 (13)
C5—O31.300 (2)
N1—Cu1—N2i93.64 (7)N3—C6—H6A120.3
N1—Cu1—O181.29 (6)C7—C6—H6A120.3
N2i—Cu1—O1172.70 (6)C6—C7—C8120.20 (19)
N1—Cu1—O3i173.89 (6)C6—C7—H7A119.9
N2i—Cu1—O3i80.46 (6)C8—C7—H7A119.9
O1—Cu1—O3i104.43 (6)C9—C8—C7117.83 (16)
N1—Cu1—O3ii92.88 (6)C9—C8—C8iii120.9 (2)
N2i—Cu1—O3ii102.51 (6)C7—C8—C8iii121.3 (2)
O1—Cu1—O3ii83.08 (5)C10—C9—C8119.79 (19)
O3i—Cu1—O3ii89.96 (5)C10—C9—H9A120.1
O2—C1—O1124.77 (18)C8—C9—H9A120.1
O2—C1—C2121.57 (17)N3—C10—C9120.04 (19)
O1—C1—C2113.66 (15)N3—C10—H10A120.0
N1—C2—C3108.88 (16)C9—C10—H10A120.0
N1—C2—C1111.66 (16)N2—N1—C2109.22 (15)
C3—C2—C1139.41 (16)N2—N1—Cu1133.39 (12)
C4—C3—C2103.99 (15)C2—N1—Cu1117.27 (13)
C4—C3—H3A128.0N1—N2—C4108.85 (15)
C2—C3—H3A128.0N1—N2—Cu1i132.90 (12)
N2—C4—C3109.06 (16)C4—N2—Cu1i118.24 (13)
N2—C4—C5111.32 (16)C10—N3—C6122.76 (17)
C3—C4—C5139.62 (17)C10—N3—H3B118.6
O4—C5—O3123.05 (17)C6—N3—H3B118.6
O4—C5—C4122.45 (16)C1—O1—Cu1115.54 (12)
O3—C5—C4114.50 (15)C5—O3—Cu1i115.29 (12)
N3—C6—C7119.33 (19)
O2—C1—C2—N1178.59 (18)O1—Cu1—N1—N2177.5 (2)
O1—C1—C2—N1−0.8 (2)O3ii—Cu1—N1—N2−99.92 (19)
O2—C1—C2—C31.8 (4)N2i—Cu1—N1—C2178.31 (15)
O1—C1—C2—C3−177.5 (2)O1—Cu1—N1—C2−6.97 (14)
N1—C2—C3—C4−0.1 (2)O3ii—Cu1—N1—C275.58 (15)
C1—C2—C3—C4176.7 (2)C2—N1—N2—C4−0.7 (2)
C2—C3—C4—N2−0.3 (2)Cu1—N1—N2—C4175.05 (15)
C2—C3—C4—C5−179.8 (2)C2—N1—N2—Cu1i−179.60 (15)
N2—C4—C5—O4176.42 (18)Cu1—N1—N2—Cu1i−3.8 (3)
C3—C4—C5—O4−4.0 (4)C3—C4—N2—N10.6 (2)
N2—C4—C5—O3−2.8 (2)C5—C4—N2—N1−179.69 (16)
C3—C4—C5—O3176.8 (2)C3—C4—N2—Cu1i179.69 (13)
N3—C6—C7—C81.8 (3)C5—C4—N2—Cu1i−0.6 (2)
C6—C7—C8—C9−2.5 (3)C9—C10—N3—C6−1.5 (3)
C6—C7—C8—C8iii176.7 (2)C7—C6—N3—C100.3 (3)
C7—C8—C9—C101.2 (3)O2—C1—O1—Cu1175.90 (16)
C8iii—C8—C9—C10−178.0 (2)C2—C1—O1—Cu1−4.8 (2)
C8—C9—C10—N30.8 (3)N1—Cu1—O1—C16.42 (14)
C3—C2—N1—N20.5 (2)O3i—Cu1—O1—C1−175.75 (13)
C1—C2—N1—N2−177.25 (16)O3ii—Cu1—O1—C1−87.58 (13)
C3—C2—N1—Cu1−176.01 (12)O4—C5—O3—Cu1i−174.44 (14)
C1—C2—N1—Cu16.2 (2)C4—C5—O3—Cu1i4.7 (2)
N2i—Cu1—N1—N22.8 (2)
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z; (iii) −x+1, −y+3, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O40.861.902.719 (2)160
Table 1
Selected geometric parameters (Å, °) top
Cu1—N11.9021 (16)Cu1—O3i1.9889 (13)
Cu1—N2i1.9099 (15)Cu1—O3ii2.7543 (15)
Cu1—O11.9647 (13)
N1—Cu1—N2i93.64 (7)O1—Cu1—O3i104.43 (6)
N1—Cu1—O181.29 (6)N1—Cu1—O3ii92.88 (6)
N2i—Cu1—O1172.70 (6)N2i—Cu1—O3ii102.51 (6)
N1—Cu1—O3i173.89 (6)O1—Cu1—O3ii83.08 (5)
N2i—Cu1—O3i80.46 (6)O3i—Cu1—O3ii89.96 (5)
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O40.861.902.719 (2)160
Acknowledgements top

The authors thank the Program for Liaoning Excellent Talents in Universities (RC-05–11) for supporting this work.

references
References top

Bruker (2001). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Chaudhuri, P. (2003). Coord. Chem. Rev. 243, 143–190.

Han, Z. B., He, Y. K., Ge, C. H., Ribas, J. & Xu, L. (2007). Dalton Trans. pp. 3020–3024.

Koomen-Van Oudenniel, W. M. E., De Graaff, R. A. G., Haasnoot, J. G., Prins, R. & Reedijk, J. (1989). Inorg. Chem. 28, 1128–1133.

La Monica, G. & Ardizzoia, G. A. (1997). Prog. Inorg. Chem. 46, 151–238.

Sears, P. & Wong, C. H. (1999). Angew. Chem. Int. Ed. 38, 2300–2324.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Tanase, S., Koval, I. A., Bouwman, E., Gelder, R. & Reedijk, J. (2005). Inorg. Chem. 44, 7860–7865.

Thompson, L. K. (2002). Coord. Chem. Rev. 233, 193–206.